EP3083232B1 - Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates - Google Patents

Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates Download PDF

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EP3083232B1
EP3083232B1 EP14812518.0A EP14812518A EP3083232B1 EP 3083232 B1 EP3083232 B1 EP 3083232B1 EP 14812518 A EP14812518 A EP 14812518A EP 3083232 B1 EP3083232 B1 EP 3083232B1
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Prior art keywords
composition
isocyanate
compounds
process according
weight
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German (de)
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EP3083232A1 (fr
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Gunnar Kampf
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BASF SE
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BASF SE
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Priority to PL14812518T priority patent/PL3083232T3/pl
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ

Definitions

  • the present invention relates to a method for producing a composite element, comprising at least the steps of providing a cover layer; Applying a composition Z1 comprising at least one isocyanate-reactive compound to the cover layer; and applying a composition Z2 suitable for producing a polyurethane and / or polyisocyanurate foam to the previously applied layer, as well as composite elements, obtainable or obtained by such a process.
  • EP 2 295 237 A1 discloses a method for producing a foam composite member comprising the steps of providing a cover layer, applying a primer layer to the cover layer, wherein the primer layer comprises a primer dispersion and applying a polyurethane and / or polyisocyanurate comprising foam layer to the primer layer.
  • the primer layer comprises a primer dispersion and applying a polyurethane and / or polyisocyanurate comprising foam layer to the primer layer.
  • the use of an aqueous polychloroprene dispersion as adhesion promoter in the production of foam composite elements is described.
  • the object of the invention was thus to generate a bonding agent for improving the adhesion of rigid polyurethane foams, especially polyisocyanurate foams, to metallic cover layers, without having to accept the above-mentioned technical disadvantages of the already existing approaches to solution.
  • the primer should be safe to health, easy to apply and still be effective even after prolonged downtime between two production phases.
  • a further object of the invention was to develop a process for the production of foam composite elements in which the adhesion between the foam core, primarily the rigid polyurethane foam core, and the cover layer, and in particular the polyisocyanurate foam core and the cover layer, is improved.
  • composition Z1 comprising isocyanate-reactive compound as adhesion promoter, which is applied before the actual foam application.
  • the process according to the invention comprises at least steps A), B) and C). However, according to the invention, the method may also comprise further steps.
  • a cover layer is provided. This can be done in continuous production facilities, for example by unwinding a rolled-up cover layer from a roll.
  • the type of cover layer can vary within wide ranges, wherein preferably the materials commonly used in the field of thermal insulation are used for cover layers.
  • the thickness of the cover layer may be, for example, 0.01 mm to 5 mm, preferably 0.05 mm to 2 mm, particularly preferably 0.1 mm to 1 mm, more specifically 0.2 mm to 0.8 mm and specifically 0.3 mm to 0.7 mm.
  • the present invention accordingly relates to a method for producing a composite element as described above, wherein the cover layer is a metal foil. According to a further embodiment, the present invention relates to a method for producing a composite element as described above, wherein the cover layer has a thickness in the range of 0.01 mm to 5.0 mm.
  • a composition Z1 comprising at least one isocyanate-reactive compound is applied to the topcoat.
  • the application can be carried out by conventional techniques such as spraying or rolling.
  • the present invention relates to a method for producing a composite element as described above, wherein the composition Z1 is applied to the cover layer by means of spraying or rolling.
  • composition Z1 contains in the context of the present invention at least one isocyanate-reactive compound. According to the invention, the composition Z1 may also contain two or more isocyanate-reactive compounds.
  • compounds which are reactive toward isocyanates are in principle suitable for all compounds which have functional groups which are reactive towards isocyanates. Particularly suitable are compounds with OH-functional groups, compounds with NH-functional groups and compounds with SH-functional groups.
  • compounds with NH-functional groups includes both primary and secondary amines.
  • the present invention accordingly relates to a method for producing a composite element as described above, wherein the at least one isocyanate-reactive compound is selected from the group consisting of compounds having OH-functional groups, compounds having NH-functional groups and compounds with SH-functional groups.
  • the at least one isocyanate-reactive compound is selected from the group consisting of compounds having OH-functional groups, compounds having NH-functional groups and compounds with SH-functional groups.
  • mixtures of two or more of the compounds mentioned can also be used according to the invention.
  • Isocyanate-reactive compounds according to the invention are particularly preferably selected from the group consisting of compounds having OH-functional groups.
  • the present invention relates to a process for producing a composite element as described above, wherein the at least one isocyanate-reactive compound is selected from the group consisting of polyethers, polyesters, compounds carrying ester and ether groups, compounds, the urethane , Ester and / or ether groups and compounds bearing urethane groups.
  • isocyanate-reactive compounds which react with isocyanates without release of gases.
  • isocyanate-reactive compounds which react neither in themselves nor with air or atmospheric moisture.
  • Isocyanate-reactive compounds are preferably polyethers and / or polyesters and / or compounds which have both ester and ether groups, and / or compounds which contain urethane, ester and / or ether functions, preferably polyethers and / or polyesters and / or compounds which contain both ester and ether groups, more preferably polyethers and / or polyesters, specifically polyethers.
  • Particularly preferred compounds of the invention are polyether polyols which are reactive toward isocyanates.
  • the polyether polyols may be prepared by known methods, for example by anionic polymerization of one or more alkylene oxides of 2 to 4 carbon atoms with alkali hydroxides such as sodium or potassium hydroxide, alkali metal alkoxides such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, or amine alkoxylation catalysts such as dimethylethanolamine ( DMEOA), imidazole or imidazole derivatives using at least one starter molecule or starter molecule mixture containing on average 2 to 8, preferably 2 to 6 reactive hydrogen atoms or prepared by cationic polymerization with Lewis acids such as antimony pentachloride, borofluoride etherate or bleaching earth , Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene
  • Suitable starter molecules are, for example, the following compounds: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N, N- and N, N'-dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical, such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4- , 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane.
  • organic dicarboxylic acids such as succinic acid,
  • Suitable starter molecules are also: alkanolamines, such as ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, such as diethanolamine, N-methyl and N-ethyldiethanolamine, and trialkanolamines, such as triethanolamine, and ammonia.
  • ком ⁇ онентs such as ethanediol, 1,2-propanediol and 1,3, diethylene glycol (DEG), dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, Trimethylolpropane, pentaerythritol, sorbitol and sucrose.
  • a starter or starter mixture having an OH functionality of less than or equal to 6, preferably less than or equal to 5, more preferably less than / equal to 4, more specifically less than or equal to 3 and in particular less than or equal to 2.
  • fatty acids or fatty acid derivatives for example fatty acid esters, to be added to the starter mixture so that some of the OH functions are esterified by the fatty acid during the alkoxylation.
  • polyesterols may be used as the isocyanate-reactive compound in the composition Z1.
  • Suitable polyester polyols may be selected from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aromatic, or mixtures of aromatic and aliphatic dicarboxylic acids and polyhydric alcohols, preferably diols and / or polyols, or alkoxylates thereof, more preferably diols and / or triols, or alkoxylates thereof , getting produced.
  • dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used both individually and in admixture.
  • the corresponding dicarboxylic acid derivatives e.g. Dicarboxylic acid esters of alcohols having 1 to 4 carbon atoms or dicarboxylic anhydrides are used.
  • aromatic dicarboxylic acids phthalic acid, phthalic anhydride, terephthalic acid and / or isophthalic acid are preferably used in admixture or alone.
  • the aliphatic dicarboxylic acids used are preferably dicarboxylic acid mixtures of succinic, glutaric and adipic acid in proportions of, for example, from 20 to 35:35 to 50:20 to 32 parts by weight, and in particular adipic acid.
  • dihydric and polyhydric alcohols in particular diols and / or triols, are: ethanediol, diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,10-decanediol, glycerol, trimethylolpropane and pentaerythritol, or their alkoxylates.
  • Polyester polyols may also be employed from lactones, e.g. epsilon-caprolactone or hydroxycarboxylic acids, e.g. ⁇ -hydroxycaproic acid.
  • polyester polyols and biobased starting materials and / or their derivatives in question such as.
  • polyesterols are used as the isocyanate-reactive compound in the composition Z1, they preferably contain less than 20% by weight, more preferably less than 15% by weight, more specifically less than 10% by weight, especially less than 5% by weight and specifically 0% by weight based on the weight of the polyesterol of fatty acids. It is also possible to use compounds in which polyesters are alkoxylated as starters according to the process already described.
  • the composition Z1 may contain one or more isocyanate-reactive compounds, in particular one or more compounds selected from the group of polyetherols and polyesterols.
  • the polyesterol content is less than 90% by weight, preferably less than 50% by weight, more preferably less than 25% by weight, more particularly less than 10% by weight, based on the mass of the isocyanate-reactive Compound in the composition Z1.
  • the isocyanate-reactive compound in the composition Z1 preferably consists exclusively of alkoxylates of a starter or of a starter mixture.
  • no polyesterols are used as the isocyanate-reactive compound in the composition Z1.
  • the molecular weight of the isocyanate-reactive compound (s) in the composition Z1 is greater than 50 g / mol, preferably greater than 150 g / mol, more preferably greater than 200 g / mol, especially greater than 400 g / mol, more specifically greater than 500 g / mol, more preferably greater than 700 g / mol and in particular greater than 900 g / mol.
  • the OH number of the isocyanate-reactive compound is less than 1500 mg KOH / g, preferably less than 1000 mg KOH / g, more preferably less than 800 mg KOH / g, more specifically less than 500 mg KOH / g, more specifically less than 300 mg KOH / g, more preferably less than 200 mg KOH / g and in particular less than 150 mg KOH / g.
  • the OH functionality of the isocyanate-reactive compound is less than or equal to 8, preferably less than or equal to 6, more preferably less than or equal to 5, more particularly less than or equal to 4, even more specifically less than or equal to 3, and more particularly less than or equal to 2.
  • the OH functionality of the isocyanate-reactive compound present in the composition Z1 is preferably greater than or equal to 1, preferably greater than or equal to 1.5.
  • the mass ratio of ethylene oxide to propylene oxide used for the preparation of the isocyanate-reactive compound present in the composition Z1 is less than or equal to 9, preferably less than or equal to 3, more preferably less than or equal to 1, more particularly less than or equal to 0.5, even more specifically less than or equal to 0.2, and more particularly less than or equal to 0.1. It is particularly preferred to use exclusively propylene oxide for the preparation of the isocyanate-reactive compound present in the composition Z1.
  • composition Z1 may comprise further compounds, for example flame retardants, blowing agents or catalysts for polyurethane or polyisocyanurate formation.
  • the composition Z1 can also contain any desired combinations of the components mentioned, for example only components (i) or (ii) or (iii) or components (i) and (ii) or components (i) and (iii) or component (ii ) and component (iii).
  • the compounds mentioned can be used in the composition Z1 in the usual amounts known to those skilled in the art.
  • the composition Z1 contains, in addition to the at least one isocyanate-reactive compound, no further compounds from group (i), (ii) or (iii). More preferably, the composition Z1 contains no further compounds besides the at least one isocyanate-reactive compound.
  • the composition Z1 may contain a blowing agent, for example a chemical or a physical blowing agent.
  • a blowing agent for example a chemical or a physical blowing agent.
  • the isocyanate-reactive compound is less than 5% by weight, preferably less than 2% by weight, more preferably less than 1% by weight, more specifically less than 0.5% by weight, especially less than 0.2% by weight. % and very particularly 0% by weight based on the mass of the isocyanate-reactive compound to chemical blowing agents, ie Compounds which react with isocyanate to form a gas, preferably water or formic acid, more preferably water added.
  • composition Z1 is preferably less than 20% by weight, preferably less than 10% by weight, more preferably less than 5% by weight, more specifically less than 1% by weight and very particularly preferably 0% by weight, based on the mass of the isocyanate reactive compound to isocyanate-unreactive, low-boiling components, so-called physical blowing agents added.
  • the composition Z1 can also be added flame retardants in any form.
  • flame retardants the flame retardants known from the prior art can generally be used. Suitable flame retardants are, for example, brominated esters, brominated ethers (xxol) or brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol, and also chlorinated phosphates such as tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate (TCPP).
  • brominated esters brominated ethers (xxol) or brominated alcohols such as dibromoneopentyl alcohol, tribromoneopentyl alcohol and PHT-4-diol
  • chlorinated phosphates such as tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate (TCPP).
  • DEEP diethyl ethane phosphonate
  • TEP triethyl phosphate
  • DMPP dimethyl propyl phosphonate
  • DPK diphenyl cresyl phosphate
  • inorganic or organic flame retardants such as red phosphorus, red phosphorus-containing finishes, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as melamine, or mixtures of at least two flame retardants, such as ammonium polyphosphates and Melamine and optionally corn starch or ammonium polyphosphate, melamine, expandable graphite and optionally aromatic polyester for flame retardancy of the rigid polyurethane foams can be used.
  • inorganic or organic flame retardants such as red phosphorus, red phosphorus-containing finishes, alumina hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate and calcium sulfate, expandable graphite or cyanuric acid derivatives, such as melamine, or mixtures of at least two flame retardants, such as ammonium polyphosphates and Melamine and optionally corn starch or ammonium poly
  • Flame retardants preferred in the present invention do not contain bromine.
  • Particularly preferred flame retardants consist of atoms selected from the group consisting of carbon, hydrogen, phosphorus, nitrogen, oxygen and chlorine, more particularly from the group consisting of carbon, hydrogen, phosphorus and chlorine.
  • Preferred flame retardants have no isocyanate-reactive groups.
  • the flame retardants used according to the invention are preferably liquid at room temperature.
  • Particularly preferred are TCPP, DEEP, TEP, DMPP and DPK, in particular TCPP.
  • composition Z1 may further include the usual PUR and PIR catalysts.
  • catalysts of the formation of urethane, or isocyanurate for example, carboxylate salts and basic, preferably amine catalysts can be used.
  • basic urethane catalysts for example tertiary amines, such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N, N ', N "-tris- (dialkylaminoalkyl) hexahydrotriazines, eg N, N', N Tris (dimethylaminopropyl) -s-hexahydrotriazine, and triethylenediamine.
  • tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine and alkanolamine compounds, such as triethanolamine, triisopropanolamine, N, N ', N "-tris- (dialkylaminoalky
  • catalysts having a carboxylate structure there may be mentioned primarily ammonium or alkali metal carboxylates, preferably alkali metal carboxylate salts, particularly preferably alkali metal formate, alkali metal acetate or alkali metal hexanoate.
  • alkali metal carboxylate salts particularly preferably alkali metal formate, alkali metal acetate or alkali metal hexanoate.
  • composition Z1 may optionally be added further auxiliaries and / or additives. Mention may be made, for example, of surface-active substances, fillers, dyes, pigments, hydrolysis protectants, fungistatic and bacteriostatic substances.
  • surface-active substances are e.g. Compounds which serve to assist the homogenization of the starting materials.
  • emulsifiers such as the sodium salts of castor oil sulfates or fatty acids, and salts of fatty acids with amines, e.g. diethylamine, stearic acid diethanolamine, diethanolamine ricinoleic acid, salts of sulfonic acids, e.g.
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkey red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpolysiloxanes.
  • Foam stabilizers such as siloxane-oxalkylene copolymers and other organopolysiloxanes, ethoxylated alkylphenols, ethoxylated fatty alcohols, paraffin oils, castor oil or ricinoleic acid esters, turkey red oil and peanut oil, and cell regulators, such as paraffins, fatty alcohols and dimethylpol
  • non-reactive solids called fillers
  • fillers can be added to the composition Z1 in any form.
  • Fillers are the conventional, customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating compositions, etc.
  • inorganic fillers such as silicate minerals, for example phyllosilicates such as antigorite, serpentine, hornblende, amphiboles, chrysotile and talc, metal oxides such as kaolin, aluminas, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide
  • kaolin China Clay
  • aluminum silicate and coprecipitates of barium sulfate and aluminum silicate and natural and synthetic fibrous minerals such as wollastonite, metal and in particular glass fibers of various lengths, which may optionally be sized.
  • Suitable organic fillers are, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers, and also cellulose fibers, polyamide, polyacrylonitrile, polyurethane, polyester fibers based on aromatic and / or aliphatic compounds. Particular preference is given to fillers which have a positive influence on the fire behavior, such as, for example, expanded graphite, gypsum, chalk, carboxylic acid esters and, in particular, carbon fibers.
  • the composition Z1 in step B) is in an amount of, for example, 1 to 1000 g / m 2 , preferably 5 to 800 g / m 2 , more preferably 10 to 800 g / m 2 , preferably 10 to 400 g / m 2 , particularly preferably 50 to 400 g / m 2 and in particular 80 to 250 g / m 2 or 20 to 250 g / m 2 and in particular 25 to 150 g / m 2 applied.
  • the present invention relates to a method for producing a composite element as described above, wherein the composition Z1 according to step B) in an amount in the range of 1 to 1000 g / m 2 is applied to the cover layer.
  • step C) of the method according to the invention a composition Z2 which is suitable for producing a polyurethane and / or polyisocyanurate foam is applied to the layer applied according to step B).
  • compositions which are suitable for producing a polyurethane and / or polyisocyanurate foam are known in principle. Suitable components are known to the person skilled in the art. Suitable components of the composition are in particular polyisocyanates and isocyanate-reactive compounds. According to a further embodiment, the present invention accordingly relates to a process for producing a composite element as described above, wherein the composition Z2 comprises at least one polyisocyanate and at least one isocyanate-reactive compound.
  • composition Z2 may contain further components.
  • the composition Z2 contains at least one isocyanate-reactive compound as component b).
  • isocyanate-reactive compounds the compounds mentioned above in connection with composition Z1 are in principle suitable.
  • Component b) preferably comprises polyethers and / or polyesters.
  • Component b) is preferably more than 10% by weight, more preferably more than 30% by weight, in particular more than 50% by weight, more specifically more than 70% by weight, even more specifically more than 80% by weight. %, more preferably more than 90% and most preferably 100% by weight based on the weight of component b) of polyesters.
  • the composition Z2 contains at least one polyisocyanate as component a).
  • a polyisocyanate is understood as meaning an organic compound which contains at least two reactive isocyanate groups per molecule, ie. H. the functionality is at least 2. If the polyisocyanates used or a mixture of several polyisocyanates have no uniform functionality, the number-weighted average of the functionality of the component a) used is at least 2.
  • Suitable polyisocyanates a) are the aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates known per se. Such polyfunctional isocyanates are known per se or can be prepared by methods known per se. The polyfunctional isocyanates can also be used in particular as mixtures, so that component a) in this case contains various polyfunctional isocyanates. Suitable polyisocyanate polyfunctional isocyanates have two (hereinafter called diisocyanates) or more than two isocyanate groups per molecule.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecanediisocyanate, 2-ethyltetramethylene diisocyanate-1,4,2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate-1,4, and preferably hexamethylene diisocyanate-1, 6; cycloaliphatic diisocyanates, such as cyclohexane-1,3- and 1,4-diisocyanate, and also any desired mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6-diisocyanate.
  • IPDI 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane
  • aromatic polyisocyanates such
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-toluene diisocyanate
  • PPDI p-phenylene diisocyanate
  • PPDI tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1 , 5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyana
  • modified polyisocyanates ie products obtained by chemical reaction of organic polyisocyanates and having at least two reactive isocyanate groups per molecule are used. Particular mention may be made of ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate and / or urethane groups-containing polyisocyanates.
  • polyisocyanates of component a) are particularly preferred as the polyisocyanates of component a): i) polyfunctional isocyanates based on tolylene diisocyanate (TDI), in particular 2,4-TDI or 2,6-TDI or mixtures of 2,4- and 2,6-TDI; ii) polyfunctional isocyanates based on diphenylmethane diisocyanate (MDI), in particular 2,2'-MDI or 2,4'-MDI or 4,4'-MDI or oligomeric MDI, which is also referred to as Polyphenylpolymethylenisocyanat, or mixtures of two or three the aforementioned diphenylmethane diisocyanate, or crude MDI, which is obtained in the preparation of MDI, or mixtures of at least one oligomer of MDI and at least one of the aforementioned low molecular weight MDI derivatives; iii) mixtures of at least one aromatic isocyanate according to embodiment i) and at least one
  • polymeric diphenylmethane diisocyanate As a polyisocyanate is very particularly preferred polymeric diphenylmethane diisocyanate.
  • Polymeric diphenylmethane diisocyanate (hereafter referred to as polymeric MDI) is a mixture of dinuclear MDI and oligomeric condensation products and thus derivatives of diphenylmethane diisocyanate (MDI).
  • the polyisocyanates may preferably also be composed of mixtures of monomeric aromatic diisocyanates and polymeric MDI.
  • Polymeric MDI contains in addition to binuclear MDI one or more polynuclear condensation products of MDI having a functionality of more than 2, in particular 3 or 4 or 5.
  • Polymeric MDI is known and is often referred to as Polyphenylpolymethylenisocyanat or as oligomeric MDI.
  • Polymeric MDI is usually composed of a mixture of MDI-based isocyanates with different functionality. Typically, polymeric MDI is used in admixture with monomeric MDI.
  • the (average) functionality of a polyisocyanate containing polymeric MDI can vary in the range of about 2.2 to about 5, more preferably 2.3 to 4, especially 2.4 to 3.5.
  • Such a mixture of MDI-based polyfunctional isocyanates with different functionalities is especially the crude MDI obtained in the production of MDI as an intermediate.
  • Polyfunctional isocyanates or mixtures of several polyfunctional isocyanates based on MDI are known and are sold, for example, by BASF Polyurethanes GmbH under the name Lupranat®.
  • the functionality of component a) is preferably at least 2, in particular at least 2.2 and particularly preferably at least 2.4.
  • the functionality of component a) is preferably from 2.2 to 4 and more preferably from 2.4 to 3.
  • the content of isocyanate groups of component a) from 5 to 10 mmol / g, in particular from 6 to 9 mmol / g, particularly preferably from 7 to 8.5 mmol / g. It is known to the person skilled in the art that the content of isocyanate groups in mmol / g and the so-called equivalent weight in g / equivalent are in a reciprocal ratio.
  • the content of isocyanate groups in mmol / g is calculated from the content in% by weight according to ASTM D-5155-96 A.
  • component a) consists of at least one polyfunctional isocyanate selected from diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate and oligomeric diphenylmethane diisocyanate.
  • component a) particularly preferably comprises oligomeric diphenylmethane diisocyanate and has a functionality of at least 2.4.
  • component a) used can vary within a wide range.
  • component a) has a viscosity of from 100 to 3000 mPa * s, more preferably from 100 to 1000 mPa * s, more preferably from 100 to 600 mPa * s, more particularly from 200 to 600 mPa * s and especially from 400 to 600 mPa * s at 25 ° C, on.
  • composition Z2 Further suitable components c) to f), which may be present in the composition Z2, are known in principle to the person skilled in the art. In particular, preferred components c) to f) according to the invention are mentioned in connection with the composition Z1.
  • the composition Z2 preferably contains the components a), b) and c), optionally d), e) and f).
  • the polyisocyanates a) are mixed with the isocyanate-reactive compounds b), the blowing agents c) and optionally further components d) to f) in amounts such that the equivalence ratio of NCO groups of the polyisocyanates a) to the sum of isocyanate-reactive hydrogen atoms of components b) to f) greater than 1: 1, preferably greater than 1.2: 1, more preferably greater than 1.5: 1, more specifically greater than 1.8: 1, even more particularly greater than 2 : 1, more specifically greater than 2.5: 1 and in particular greater than 3: 1.
  • the equivalence ratio of NCO groups of the polyisocyanates a) to the sum of the isocyanate-reactive hydrogen atoms of the components b) to f) is less than 10: 1, preferably less than 8: 1, more specifically less than 6: 1, more particularly less than 5: 1, more specifically less than 4.5: 1, in particular less than 4: 1 and especially less than 3.5: 1.
  • composition Z2 according to step C) can also be carried out in a continuous production plant.
  • This layer may, for example, have a thickness of 0.5 cm to 30 cm, preferably 2 cm to 22 cm and particularly preferably 12 cm to 20 cm.
  • the present invention relates to a method for producing a composite element as described above, wherein the layer applied according to step C) has a thickness in the range of 0.5 to 30 cm.
  • a method for applying a composition which is suitable for producing a polyurethane and / or polyisocyanurate foam are known in principle to the person skilled in the art.
  • reaction components for the foam formation are mixed only immediately before application in a mixing head and the composition Z2 is applied immediately afterwards to the layer formed from the composition Z1 so that foaming takes place on the cover layer provided with the composition Z1 .
  • the use of the so-called double-belt method for producing the composite elements is advantageous because they have good flame retardancy even with a reduced flame retardant.
  • a further layer can be applied, in particular a cover layer. Since usually the adhesion to the upper cover layer used in the process, which is optionally applied according to step D), is sufficiently good even without the use of an adhesion promoter, it is preferred in the context of the present invention that no adhesion promoter be applied between the layer applied according to step C) and the cover layer applied according to step D) is used.
  • the present invention relates to a method for producing a composite element as described above, the method comprising a step D): D) applying a cover layer to the layer applied according to step C).
  • the further covering layer it is possible for the further covering layer to be applied before complete curing of the layer applied according to step C).
  • the further outer layer it is also possible according to the invention for the further outer layer to be applied after the complete curing of the layer applied according to step C), for example using an adhesive layer.
  • the further covering layer may be the same or different from the first covering layer. It is likewise preferably a metal foil, the thickness also being in the usual ranges, for example 0.01 mm to 5 mm, preferably 0.05 mm to 2 mm, particularly preferably 0.1 mm to 1 mm, more specifically 0, 2 mm to 0.8 mm and specifically 0.3 mm to 0.7 mm.
  • the present invention relates to a method for producing a composite element as described above, wherein the second cover layer is a metal foil and wherein the cover layer preferably has a thickness in the range of 0.01 mm to 5.0 mm.
  • the present invention also relates to composite elements obtainable or obtained by a method for producing a composite element as described above.
  • the composite elements according to the invention have a high stability due to the good adhesion between the cover layer and the foam layer.
  • composition Z1 acts as a bonding agent between the cover layer of the composite element and the polyurethane and / or Polyisocyanuratschaum für. Therefore, the present invention also relates to the use of a composition Z1 comprising at least one isocyanate-reactive compound as described above as adhesion promoter in a process for producing a composite element comprising at least one cover layer and at least one polyurethane and / or polyisocyanurate foam layer.
  • the isocyanates as well as the isocyanate-reactive components were foamed together with the blowing agents, catalysts and all other additives at a constant mixing ratio of polyol component to isocyanate of 100: 180.
  • Polyesterol consisting of the esterification product of phthalic anhydride, diethylene glycol and oleic acid having a hydroxyl functionality of 1.8 and a hydroxyl number of 235 mg KOH / g.
  • the samples were stored after preparation for 24 hours at room temperature (18 to 22 ° C). Subsequently, one of the pieces of sheet metal was pulled manually from the foam and the peel adhesion assessed qualitatively.
  • the second sample ie the second foamed piece of sheet steel, was used to determine the tensile strength according to DIN 53292 / DIN EN ISO 527-1. Important for the assessment of the element tensile strengths determined in this way is the consideration of the fracture zone. If, in the determination of the tensile strength, the foam is to be detached from the cover layer, ie the break zone lies in the interface between the cover layer and the foam, then the tensile strength corresponds to the adhesive strength between foam and cover layer and thus the adhesion of the foam to the cover layer.

Landscapes

  • Polyurethanes Or Polyureas (AREA)

Claims (19)

  1. Procédé de fabrication d'un élément composite, comprenant au moins les étapes suivantes :
    A) la préparation d'une couche de recouvrement ;
    B) l'application d'une composition Z1 contenant au moins un composé réactif avec les isocyanates sur la couche de recouvrement ;
    C) l'application d'une composition Z2, qui est appropriée pour la fabrication d'une mousse de polyuréthane et/ou de polyisocyanurate, sur la couche appliquée selon l'étape B),
    la composition Z1 contenant moins de 5 % en poids, par rapport à la masse du composé réactif avec les isocyanates, de composés qui réagissent avec les isocyanates avec formation d'un gaz.
  2. Procédé selon la revendication 1, dans lequel la composition Z1 contient moins de 0,2 % en poids, par rapport à la masse du composé réactif avec les isocyanates, de composés qui réagissent avec les isocyanates avec formation d'un gaz.
  3. Procédé selon la revendication 1 ou 2, dans lequel moins de 5 % en poids, par rapport à la masse du composé réactif avec les isocyanates, de composants de point d'ébullition faible, non réactifs avec les isocyanates, sont ajoutés à la composition Z1.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel l'au moins un composé réactif avec les isocyanates est choisi dans le groupe constitué par les composés contenant des groupes à fonction OH, les composés contenant des groupes à fonction NH et les composés contenant des groupes à fonction SH.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'au moins un composé réactif avec les isocyanates est choisi dans le groupe constitué par les polyéthers, les polyesters, les composés qui portent des groupes ester et éther, les composés qui portent des groupes uréthane, ester et/ou éther, et les composés qui portent des groupes uréthane.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la fonctionnalité OH du composé réactif avec les isocyanates est inférieure ou égale à 3 et supérieure ou égale à 1.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel la composition Z1 est appliquée sur la couche de recouvrement selon l'étape B) en une quantité dans la plage allant de 1 à 1 000 g/m2.
  8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel la composition Z1 contient un ou plusieurs des composants suivants :
    (i) des agents ignifuges ;
    (ii) des agents gonflants ;
    (iii) des catalyseurs pour la formation de polyuréthanes ou de polyisocyanurates.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel la composition Z2 contient au moins un polyisocyanate et au moins un composé réactif avec les isocyanates.
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel la composition Z2 contient les composants suivants :
    a) au moins un polyisocyanate ;
    b) au moins un composé réactif avec les isocyanates :
    c) au moins un agent gonflant.
  11. Procédé selon l'une quelconque des revendications 1 à 10, dans lequel la composition Z2 contient un ou plusieurs des composants suivants :
    d) des agents ignifuges,
    e) des catalyseurs pour la formation de polyuréthanes ou de polyisocyanurates,
    f) des adjuvants ou additifs supplémentaires.
  12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel la composition Z1 est appliquée par pulvérisation ou cylindrage sur la couche de recouvrement.
  13. Procédé selon l'une quelconque des revendications 1 à 12, dans lequel la couche appliquée selon l'étape C) présente une épaisseur dans la plage allant de 0,5 à 30 cm.
  14. Procédé selon l'une quelconque des revendications 1 à 13, dans lequel le procédé comprend une étape D) :
    D) l'application d'une couche de recouvrement sur la couche appliquée selon l'étape C).
  15. Procédé selon l'une quelconque des revendications 1 à 14, dans lequel la couche de recouvrement est une feuille métallique.
  16. Procédé selon l'une quelconque des revendications 1 à 15, dans lequel la couche de recouvrement présente une épaisseur dans la plage allant de 0,01 mm à 5,0 mm.
  17. Élément composite, pouvant être obtenu ou étant obtenu par un procédé selon l'une quelconque des revendications 1 à 16.
  18. Utilisation d'une composition Z1 contenant au moins un composé réactif avec les isocyanates en tant que promoteur d'adhésion dans un procédé pour la fabrication d'un élément composite comprenant au moins une couche de recouvrement et au moins une couche de mousse de polyuréthane et/ou de polyisocyanurate,
    le procédé comprenant les étapes A) à C) :
    A) la préparation de la couche de recouvrement ;
    B) l'application de la composition Z1 contenant au moins un composé réactif avec les isocyanates sur la couche de recouvrement ;
    C) l'application d'une composition Z2, qui est appropriée pour la fabrication de la mousse de polyuréthane et/ou de polyisocyanurate, sur la couche appliquée selon l'étape B),
    la composition Z1 contenant moins de 5 % en poids, par rapport à la masse du composé réactif avec les isocyanates, de composés qui réagissent avec les isocyanates avec formation d'un gaz.
  19. Utilisation selon la revendication 18, dans laquelle la composition Z1 contient moins de 0,2 % en poids, par rapport à la masse du composé réactif avec les isocyanates, de composés qui réagissent avec les isocyanates avec formation d'un gaz.
EP14812518.0A 2013-12-19 2014-12-16 Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates Active EP3083232B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP14812518.0A EP3083232B1 (fr) 2013-12-19 2014-12-16 Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates
PL14812518T PL3083232T3 (pl) 2013-12-19 2014-12-16 Sposób wytwarzania elementów kompozytowych ze sztywnego tworzywa piankowego z reaktywnymi względem izocyjanianu promotorami adhezji

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13198526 2013-12-19
PCT/EP2014/077915 WO2015091451A1 (fr) 2013-12-19 2014-12-16 Procédé de production d'éléments composites à base de mousse dure au moyen d'agents adhésifs réactifs vis-à-vis des isocyanates
EP14812518.0A EP3083232B1 (fr) 2013-12-19 2014-12-16 Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates

Publications (2)

Publication Number Publication Date
EP3083232A1 EP3083232A1 (fr) 2016-10-26
EP3083232B1 true EP3083232B1 (fr) 2019-08-14

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EP14812518.0A Active EP3083232B1 (fr) 2013-12-19 2014-12-16 Procédé de fabrication d'éléments composites en mousse rigide à l'aide d'agents adhésifs réactifs aux isocyanates

Country Status (6)

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EP (1) EP3083232B1 (fr)
ES (1) ES2755153T3 (fr)
LT (1) LT3083232T (fr)
PL (1) PL3083232T3 (fr)
PT (1) PT3083232T (fr)
WO (1) WO2015091451A1 (fr)

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Publication number Priority date Publication date Assignee Title
US11472152B2 (en) 2017-05-30 2022-10-18 Basf Se Method for producing insulated pipes

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Publication number Priority date Publication date Assignee Title
EP2295237A1 (fr) * 2009-09-14 2011-03-16 Bayer MaterialScience AG Procédé de fabrication d'un élément composite en mousse à l'aide d'une dispersion d'agent adhésif

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Also Published As

Publication number Publication date
ES2755153T3 (es) 2020-04-21
EP3083232A1 (fr) 2016-10-26
PL3083232T3 (pl) 2020-03-31
PT3083232T (pt) 2019-11-04
WO2015091451A1 (fr) 2015-06-25
LT3083232T (lt) 2019-11-11

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